Metalworking lubricant



United States Patent ()ifice 2,993,858 Patented July 25, 1961METALWORKING LUBRICANT Louis Sudholz, Flushing, N.Y., assignor t SoconyMObll Oil Company, Inc., a corporation of New York No Drawing. FiledApr. 10, 1958, Ser. No. 727,532 9 Claims. (Cl. 252-325) This inventionhas to do with lubricants and, more particularly, with compositionsespecially adapted for lubricating metals during processing operationssuch as cutting including broaching, turning, threading, drilling,tapping, and milling, and operations such as grinding, drawing, rollingand the like. These are generally referred to in the art as metalprocessing oils.

Such oils are used by flowing over the tool and the work in a steadystream, and function to dissipate the heat from both the tool and thework; improve tool life; improve the quality of the surface produced;lubricate the surfaces in contact between the tool and the work; washaway the chips; decrease tool wear; decrease friction between chip andtool; and provide lubrication between the chip and the tool, thusreducing the effect of the high pressure of the chip on the tool. Thereis ordinarily an enormous pressure exerted between the cutting edge ofthe tool and the metal being machined and in addition, due to theinherent resiliency of the metal, heavy pressures are maintained betweenthe work and the surf-ace of the tool just under the cutting edge andbetween the chips and the surface of the tool just back of the cuttingedge. Therefore, it is requisite that a lubricant be provided which iscapable of affording a high load-carrying lubricant film between thecutting tool, chip and the work being machined.

Dependent upon the type of metals being processed or the design of themachine used, a corrosive oil or a noncorrosive oil is utilized. Thatis, with copper, brass or bronze, a non-corrosive lubricant should beselected, because corrosive lubricants stain such metals. When wroughtiron or steel is concerned, a corrosive lubricant can be used. Machineshaving bronze gibs and slides which would be exposed to the action ofthe lubricant, require non-corrosive lubricants when in use, sincecorrosion would cause the slides to stick; the machines would then haveto be shut down and cleaned.

Corrosive cutting oils can be defined as those which cause more than aslight discoloration in the copper strip test. This test involvesimmersion of a copper strip in the test oil or composition for threehours at 212 F. Non-corrosive cutting oils can be defined as those whichcause no more than slight discoloration of a copper strip under suchtest conditions.

It has heretofore been the practice to improve the film strength ofcorrosive and non-corrosive cutting oils by the incorporation therein ofvarious compounds of sulfur, phosphorus, chlorine, metal, fattymaterials or combinations thereof. Such additive materials, however,have not been found to be entirely satisfactory because of a variety ofshortcomings. Materials containing high concentrations of active sulfurare disadvantageous since they tend to cause corrosion and/or stainingof certain metals when in contact therewith at relatively lowtemperatures. Halogen-containing additives, particularly chlorinatedmaterials, may cause staining under humid conditions and often losehalogen (as chlorine) during use. Many phosphorus-containing additives,such as acid esters of phosphorus, combine with iron fines during use(particularly grinding operations) and form iron soaps which increasethe viscosity of the oil and promote excessive foam formation.

Accordingly, it is an object of the present invention to provideimproved lubricants for lubrication during metal processing operations,such lubricants being free of the aforementioned shortcomings.

Another object is to provide cutting oils characterized by a high degreeof machining efiiciency. A further object is to provide improvednon-corrosive type cutting oils. Still another object is to providecorrosive cutting oils. Other objects will be apparent from thefollowing description.

The foregoing objects are realized with a mineral oil compositioncontaining in combination a corrosive sulfurcontaining extreme pressureagent or a non-corrosive extreme pressure agent, and an oil-soluble,phosphorus-, sulfurand metal-containing reaction product prepared by:(1) forming a mixture of a hydrocarbon material, such as a petroleumoil, and a metal hydroxide; (2) contacting said mixture with anoxidizing gas at a temperature of from about C. to about 325 C. toprovide a metalcontaining oxidized hydrocarbon product; (3) reacting themetal-containing oxidized hydrocarbon product with a phosphorus sulfideto provide a metal-, phosphorusand sulfur-containing oxidizedhydrocarbon product; (4) forming a mixture of the product produced in(3) with water and a metal hydroxide, at a temperature below the boilingpoint of water; (5) substantially completely dehydrating the mixtureformed in (4); and (6) filtering the dehydrated mixture from (5) toremove insolubles therefrom.

Details for the character and preparation of the aforesaid reactionproduct are provided in application Serial No. 554,390, filed December23, 1955 by H. G. Berger et al., now issued as Patent No. 2,830,949, andsuch details are incorporated herein by reference. For the sake ofbrevity, it may be pointed out that the hydrocarbon starting materialsthus incorporated herein by reference may be briefly characterized aspetroleum oils having a molecular weight of from about 200 to 1000 andwhich are selected from the group consisting of aliphatic hydrocarbonsand aromatic hydrocrabons having at least one nuclear hydrogen atomsubstituted by an aliphatic radical to provide a total of at least 8aliphatic carbon atoms per molecule therein, and mixtures thereof.However, a typical and preferred reaction product is described in detailhereinafter by way of illustration. These reaction products have anunusually high metal content, and were found by Berger et al. to exhibitexceptional detergent properties as well as antioxidant activity.

As indicated above, in addition to the high metalcontent reactionproduct present in the cut-ting oils of this invention, there is alsopresent one or more other characterizing extreme pressure componentsdepending upon the desired character of the lubricant-that is, corrosiveor non-corrosive. Corrosive cutting oils as contemplated herein willcontain one or more sulfur-containing organic compositions in which thesulfur is loosely bound. As considered herein loosely bound sulfur isthat which will cause more than a slight discoloration on a copper stripin the copper strip test identified above. It is to be understood thatin addition to having looselybound sulfur, the sulfur-containing organiccompositions can contain one or more other characterizing elements suchas bromine, chlorine, phosphorus, oxygen and nitrogen.

Representative of corrosive, sulfur-containing organic compositions inwhich sulfur is loosely-bound" are the following: sulfurized animal,marine and vegetable oils containing from about 12 to about 20 percentof sulfur; sulfurized mineral oil containing up to about 5 percent ofadded sulfur; sulfurized terpenes, organic polysulfides and mercaptans.Of such agents, particularly preferred are sulfurized lard and spermoils containing about 15 percent by weight of sulfur.

It is also to be understood that the mineral oil base of the cutting oilcan be sulfurized such that the sulfur therein is loosely-bound, inwhich case the cutting oil will be corrosive. When such a sulfurizedmineral oil base is used, the cutting oil need not, but may, contain aseparate sulfur-containing extreme pressure agent. Illustrative of suchsulfurized base oils are parafiinic and naphthenic oils havingviscosities from about 40 to about 300 seconds (SUS) at 100 F., andsulfurized to contain between about 0.1 and about 5 percent of sulfur.

Non-corrosive cutting oils of this invention contain non-corrosiveextreme pressure agents which are characterized by firmly-bound sulfur,phosphorus, and/or halogen such as chlorine and bromine. Typical of suchagents are: sulfurized animal, marine and vegetable oils containing upto about percent by weight of sulfur; dibenzyl disulfide; chlornaphthaxanthate; chlorinated fatty materials such as chlorinated stearic acids;chlorinated waxes; organic phosphorus compounds such as thiophosphates;etc. Preferred of such agents are sulfurized lard and sperm oilscontaining about 10 percent by weight of sulfur.

Illustrative and preferred of the high metal content reaction productsidentified above, is the following product described in Example 1.

EXAMPLE 1 Two thousand grams of a percolated, solvent refinedMid-Continent type bright stock (average molecular weight, about 800)and 200 grams (9.1 weight percent) of hydrated lime (available calciumoxide, 70% minimum) weremixed and then charged to an electrically heatedglass column (60 feet in length, 3 inches in diameter). The column has afritted glass disc sealed in the bottom for air dispersion. The contentsof the column were heated rapidly to 425 F. Air was introduced throughthe glass frit at a rate of 3 liters per hour per 100 grams of oil forabout 21 hours. The product thus formed was filtered. The filtrate has acalcium content from about 1.5-1.7 percent by weight.

The filtered oxidized oil is charged to a glass flask equipped with astirrer, thermometer and a nitrogen inlet tube. The oil was diluted withan equal weight of a dilution oil; this is a paraffinic oil having: anA.P.I. gravity of 27.5; an S.U.S. viscosity at 100 F. of 100-110; aflash (C.O.C., F.) of 350, minimum; and a color (A.S.T.M.) of 2,maximum. About 10 percent by weight of P 8 based upon the bright stockcharge, is added to the diluted oxidized oil, and the resulting mixturewas reacted at 300 F. for 2 hours in an atmosphere of nitrogen.Following this, the reaction mixture was cooled to 170- 180 F. and wastreated with 10 percent by weight of water, and then with 10 percent byweight of hydrated lime; the quantities of water and of lime are basedupon the bright stock charge. The mixture thus formed was dehydratedwhen heated to a temperature of 300 F.; it was maintained at 300 F. forone hour. Five percent by weight of Hyflo (filter aid) was added and theproduct was filtered hot through a Hyflo coated, electrically heatedfunnel. The filtrate, representing the desired reaction product in thedilution oil (1:1 dilution), has an analysis of the following character:

Percent Calcium 1.5-2.8 Phosphorus 0.9-1.4 Sulfur 1.5-3.0

A reaction product so prepared is shown in several tests hereinafter andis identified as Reaction Product A.

It has also been found that the dehydrated product can be used in thecutting oils of this invention, thus dispensing with the filtrationstep.

Although a wide range of mineral lubricating oils can be used as thebase for the cutting oils described herein, in general the oil is onehaving a Saybolt Universal viscosity at 100 F. in the range of from 40to about 500 seconds and an A.P.I. gravity of 15 to 36. However, inpreparing the new compositions, it is preferred to use one having aviscosity range of 50-350 seconds and a gravity range of l8-36.Correspondingly, with corrosive cutting oils having a sulfurized mineraloil base, it is preferred that the base oil contain from about 0.1 toabout 5% by weight of loosely bound" sulfur and be one prepared bysulfurizing a mineral oil having a viscosity range of 40- 300 seconds at100 F. and a gravity range of 18-36.

The concentration of the high metal-content reaction product in thecutting oils of this invention, is such as to improve the machiningefiiciency thereof and can be varied considerably in accordance to theuse to which they are put. When the cutting oils are employed ascoolants, as well as lubricants and are applied by a circulating pump orthe like, the reaction product should ordinarily be present in aconcentration of from about 1 percent to about 9 percent by weight.Where the cutting oils are applied to the work and tool by brushing orthe like, the reaction product will be present in a concentration offrom 10 percent to 20 percent by weight.

The compositions of this invention, therefore, comprise the combinationof the following components:

Broad Preferred range, range.

weight weight percent percent Corrosive cutting oils:

(a) Mineral oil 60-98 94 Corrosive extreme pressur agent 1-20 3 Reactionproduct A 1-20 3 (b) Sulfurized mineral oil cont loosely-bound sulfur-90 94 Reaction product A 1 -20 6 (c) sulfurized mineral 011 containing"loosely-bound" sulfur 60-98 J4 Corrosive extreme pressure agent 1-20 3Reaction product A l-20 3 Non-corrosive cutting oils:

) Mineral oil 80-93 1:4

N on-corrosive extreme pressure agent... 1-10 3 Reaction product A i-lt)3 The foregoing concentrations are balanced in order that the cuttingoils have the desired combination of properties. That is, if too little,less than about one percent by weight of reaction product is present inthe corrosive and noncorrosive cutting oils, the said cutting oils aredeficient in certain machining operations such as tapping efiiciency.correspondingly, when too large a concentration of extreme pressureagent and reaction product is used, machining efficiency is lowered.This is illustrated hereinafter by test data.

The compositions of this invention have proven to be advantageous in anumber of respects, as is shown by the following tests and test data.

Almen pin test This test is described in Proc. A.P.l., 1932, pages 118-130.

Tapping efiiciency In the measurement of tapping efficiency of an oil, aseries of holes is accurately drilled in a test metal,

namely SAE 1020 hot rolled steel. These holes are subsequently tappedwith a series of taps in a drill press equipped with a table, which isfree to rotate about the center, being mounted on ball bearings. Atorque arm is attached to this floating table and this arm in turnactuates a spring scale so that the actual torque during tapping withthe oil being evaluated is measured directly. The same taps used inevaluating the test oil are employed in tapping with a standardreference oil, which has arbitrarily been assigned an efiiciency of 100percent. The average torque for the test oil is compared to that of thestandard and a relative efliciency is calculated on a percentage basis.For example,

Torque with standard reference oil 19.3 Torque with test oil 19.8

Relative efiiciency of test oil This test is described by C. D. Flemmingand applicant in Lubrication Engineering, vol. 12, No. 3, May- June1956, pages 199-203.

Test results correlate well with actual field conditions.

Falex snap test This test is described in Bulletin No. 3, Faville LeVally Corporation, Chicago, Illinois.

TABLE I NON-CORROSIVE CUTTINGOOIILLS, ADDITIVES IN MINERAL Cone, TappingFalex Almen Additives pereifisnap, pin,

cent ciency, lbs. p.s.l. wt. percent None 60 1, 000 1, 000 Reactionproduct A. 3 69 3, 000 4, 000 Non-corrosive sulfurized fat 3 75 2, 7508, 500 R 1111). .ENFX. g 79 3, 375 17, 500

eac on pro uc Non-corrosive sulfurized fat 3 82 30'000+ Brigzgt stock,135 secs. g 60 1, 000 2,000

o. Non-corrosive sulfurizcd fat 3 74 750 000 B Non-corrosive sulfurizedfat is a sulfurized lard 011 containing 10 percent by weight of sulfur.

b Bright stock is a solvent-refined paraffimc oil having a viscosity of135 seconds (SUB) at 100 F.

TABLE II OORROSIVE CUTTING OILS, ADDITIVES IN SULFURIZED MINERAL OILCone, Tapping Falex Almen Additives pereifisnap, pin,

cent clency, lbs. p.s.1. wt. percent None 90 1, 750 15, 000 Brightstock, 135 secs. 3 93 1, 875 16, 000 Oxidized bright stock plus Ca 3 991, 750 30, 000+ Reaction product A.-- 3 100 2, 175 30, 000+ D 6 104 2,000 30, 000+ Corrosive sulfurized fat 3 104 2, 760 500 Do 6 108 3, 12520,000 Commercial heavy duty sulfurized-chlorinated cutting oil 1 104 2,775 30, 000+ Reaction product A 3 Corrosive sulfurizcd fat 3 n5 250 000+b Identified in Table I.

B Snlfurized mineral oil is a naphthenic oil having a viscosity of 150secpnds (S.U.S.) at 100 F., suliin-ized to contain one percent of addedan or.

Oxidized bright stock plus Ca is an intermediate product formed in thepi lgaration of Reaction Product A; it is the product which is reactedWith 2 5.

Corrosive suliurized fat is a sulfurized lard oil containing 15 percentby weight of sulfur. v I

f Commercial heavy duty sulfnrized-clilorinated cutting 011 comprisessnliurized mineral oil (c), 5 percent by weight of chlorinated parafiinwax (10 1pei cent chlorine content) and 2 percent by weight ofhydroabietyl a co As mentioned above, the reaction products and theextreme pressure agents of the new compositions are used 6 in properconcentrations in order to obtain the desired results. This isillustrated in Table III below:

TABLE III CORROSIVE CUTTING OILS, ADDITIVES IN SULFURIZED MINERAL OILReaction Conc., Corrosive Cone, Tapping product wt. sulfurized wt.etficiency,

A percent fat 8 percent percent I 6 111 v 1 v 6 113 M 3 6 115 v 6 6 110e Identified in Table II.

In addition the foregoing test data, one experimental corrosive cuttingoil has been tested extensively for pipe threading in a commercial pipeshop. The experimental oil has outperformed a black pipe threading oilwhich had been used commercially for many years with success. Verylittle wear of the threading tool (chaser) resulted. The experimentaloil has been used on many sizes of pipe, ranging from /2 inch to 2 inch,and on many types of pipe, such as galvanized, black iron, malleableiron and brass. The experimental oil comprises: 94 percent by weight ofsulfurized mineral oil, 3 percent of Reaction Product A and 3 percent ofcorrosive sulfurized fat. The sulfurized mineral oil and sulfurized fatare the same as those identified above in Table II.

The same experimental oil used in pipe threading, was used in tapping ofstainless steel (type 321). High speed steel taps (2 inch) were used.With this oil, tapping speeds five to ten times the speeds recommendedby the tool manufacturer were realized. At the end of one monthsoperation with the oil, there was no wear on the tool. In a three weektest involving thread grinding of inch-20 high speed steel taps, theexperimental oil was found to be at least equivalent to more expensiveconnnercial oils in regard to finish of the tap and low grinding wheelwear. The experimental oil was superior, however, in that no foamingthereof occurred during use, whereas some other oils foamed.

I claim:

1. Cutting oil composition consisting essentially of about 94. percentby weight of mineral oil, about 3 percent by weight of (A) a sulfurizedlard oil containing about 15 percent by weight of sulfur, and about 3percent by weight of (B) an oil-soluble, phosphorus-, sulfurandcalcium-containing oxidized hydrocarbon reac-- tion pro-duct produced bythe method which comprises the steps of: (1) forming a mixturecomprising (a) a petroleurn oil having a molecular weight of from: about200 to 1000 and which is selected from the group consisting of aliphatichydrocarbons and aromatic hydrocarbons having at least one nuclearhydrogen atom substituted by an aliphatic radical to provide a total ofat least 8 aliphatic carbon atoms per molecule therein, and mixturesthereof, and (b) from about 0.5 percent to about 25 percent, based onthe weight of said petroleum oil, of calcium hydroxide; (2) contactingsaid mixture with air at a temperature of from about C.to about 325 C.to eifect oxidation of said petroleum oil and reaction of said calcium.hydroxide with the oxidized petro leurn oil; (3) continuing theoxidation for a time sufficient to incorporate from about 0.05 percentto about 3.0 percent by weight, of calcium into the oxidized petroleumoil; (4) reacting the product from (3 with from about 5 percent to about20 percent by weight, based on the weight of the petroleum oil chargedin (l), of P 3 at a temperature of from about 75 C. to about 150 C. toform a phosphorus-, sulfurand calciumcontaining product; (5) providing amixture ofthe reaction product from (4) with from about 2 percent toabout 25 percent by weight, based on the petroleum oil charged in 1), ofcalcium hydroxide, and water, at a temperature below the boiling pointof water; (6) substantially completely dehydrating the mixture formed in(5); and (7) subjecting the dehydrated mixture to filtration to removeinsolubles therefrom.

2. Cutting oil composition consisting essentially of a sulfurizedmineral oil containing from about 0.1 to about 5 percent by weight ofsulfur, in loosely-bound form adapted to effect a substantialdiscoloration of a copper strip when said strip is immersed in thecomposition for three hours at 212 F., and having incorporated thereinfrom about 1 to about 20 percent by weight of the oil soluble,phosphorus-, sulfurand calcium-containing reaction product defined as(B) in claim 1.

3. Cutting oil composition consisting essentially of about 94 percent byweight of a sulfurized mineral oil containing about one percent byweight of sulfur, in loosely-bound form adapted to effect a substantialdiscoloration of a copper strip when said strip is immersed in thecomposition for three hours at 212 F., and having incorporated thereinabout 3 percent by weight of (A) a sulfurized lard oil containing aboutpercent by weight of sulfur, and about 3 percent by weight of (B) anoilsoluble, phosphorus-, sulfurand calcium-containing oxidizedhydrocarbon reaction product produced by the method which comprises thesteps of: (1) forming a mixture comprising (a) a petroleum oil having amolecular weight of from about 200 to 1000 and which is selected fromthe group consisting of aliphatic hydrocar hens and aromatichydrocarbons having at least one nuclear hydrogen atom substituted by analiphatic radical to provide a total of at least 8 aliphatic carbonatoms per molecule therein, and mixtures thereof, and (b) from about 0.5percent to about 25 percent, based on the weight of said petroleum oil.of calcium hydroxide; (2) contacting said mixture with air at atemperature of from about 125 C. to about 325 C. to effect oxidation ofsaid petroleum oil and reaction of said calcium hydroxide with theoxidized petroleum oil; (3) continuing the oxidation for a timesufficient to incorporate from about 0.05 percent to about 3.0 percentby weight, of calcium into the oxidized petroleum oil; (4) reacting theproduct from (3) with from about 5 percent to about percent by Weight,based on the weight of the petroleum oil charged in (l), of P 8 at atemperature of from about 75 C. to about 150 C. to form a phosphorus-,sulfurand calcium-containing product; (5) pro viding a mixture of thereaction product from (4) with from about 2 percent to about percent byweight, based on the petroleum oil charged in 1), of calcium hydroxide,and water, at a temperature below the boiling point of water; (6)substantially completely dehydrating the mixture formed in (5); and (7)subjecting the dehydrated mixture to filtration to remove insolublestherefrom.

4. Cutting oil composition consisting essentially of mineral oil havingincorporated therein from about 1 to about 20 percent by weight of (A)an oil-soluble, sulfurcontaining, non-corrosive organic film strengthagent selected from the group consisting of animal, marine, andvegetable oils, each containing about 1 to 10 percent by weight ofsulfur in firmly bound form adapted to effect no substantialdiscoloration of a copper strip when said strip is immersed in thecomposition for three hours at 212 F., and from about 1 to about 20percent by weight of (B) the oil-soluble, phosphorus-, sulfurandcalciumcontaining reaction product defined as (B) in claim 1.

5. Cutting oil composition consisting essentially of a sulfurizedmineral oil containing from about 0.1 to about 5 percent by weightsulfur, in loosely-bound form adapted to effect a substantialdiscoloration of a copper strip when said strip is immersed in thecomposition for three hours at 212 F., and having incorporated thereinfrom about 1 to about 20 percent by weight of the oil-soluble,phosphorus-, sulfurand calcium-containing reaction product defined as(B) in claim 1, and from about 1 to about 20 percent by weight of anoil-soluble, corrosive extreme pressure agent selected from the groupconsisting of a parafi'inic oil having a viscosity of about 40 to 300seconds (SUS) at F., and sulfurized to contain between about 0.1 andabout 5 percent of sulfur, a naphthenic oil having a viscosity of about40 to 300 seconds (SUS) at 100 F. and sulfurized to contain betweenabout 0.1 and about 5 percent of sulfur, an animal oil containing about12 to about 20 percent of sulfur, a marine oil containing about 12 toabout 20 percent of sulfur and a vegetable oil containing about 12 toabout 20 percent of sulfur.

6. Cutting oil compositon as defined by claim 5 wherein the extremepressure agent is a sulfurized sperm oil containing about 15 percent byweight of sulfur.

7. Cutting oil composition as defined by claim 5 wherein the extremepressure agent is a sulfurized lard oil containing about 15 percent byweight of sulfur.

8. Cutting oil composition consisting essentially of about 94 percent byweight of a sulfurized mineral oil containing about 1 percent by weightof sulfur, in loosely-bound form adapted to effect a substantialdiscoloration of a copper strip when said strip is immersed in thecomposition for three hours at 212 F., and having incorporated thereinabout 6 percent by weight of (B) an oil-soluble, ph0sphorus-, sulfurandcalcium-containing oxidized hydrocarbon reaction product produced by themethod which comprises the steps of: (l) forming a mixture comprising(a) a petroleum oil having a mo lecular weight of from about 200 to 1000and which is selected from the group consisting of aliphatichydrocarbons and aromatic hydrocarbons having at least one nuclearhydrogen atom substituted by an aliphatic radical to provide a total ofat least 8 aliphatic carbon atoms per molecule therein, and mixturesthereof, and (b) from about 0.5 percent to about 25 percent, based onthe weight of said petroleum oil, of calcium hydroxide; (2) contactingsaid mixture with air at a temperature of from about C. to about 325 C.to effect oxidation of said petroleum oil and reaction of said calciumhydroxide with the oxidized petroleum oil; 3) continuing the oxidationfor a time sufficient to incorporate from about 0.05 percent to about3.0 percent by weight,-

of calcium into the oxidized petroleum oil; (4) reacting the productfrom 3) with from about 5 percent to about 20 percent by weight, basedon the weight of the petroleum oil charged in (l), of P 8 at atemperature of from about 75 C. to about C. to form a phosphorus-, andsulfurand calcium-containing product; (5) providing a mixture of thereaction product from (4) with from about 2 percent to about 25 percentby weight, based on the petroleum oil charged in (1), of calciumhydroxide, and water, at a temperature below the boiling point of water;(6) substantially completely dehydrating the mixture formed in (5); and(7) subjecting the dehydrated mixture to filtration to remove insolublestherefrom.

9. Cutting oil composition consisting essentially of about 94 percent byweight of a mineral oil and having incorporated therein about 3 percentby weight of (A) a non-corrosive, sulfurized lard oil containing about10 percent by weight of sulfur and adapted to effect no substantialdiscoloration of a copper strip when said strip is immersed in thecomposition for 3 hours at 212 F., and about 3 percent by weight of (B)an oil-soluble, phosphorus-, sulfurand calcium-containing oxidizedhydrocarbon reaction product produced by the method which comprises thesteps of: (1) forming a mixture comprising (a) a petroleum oil having amolecular weight of from about 200 to 1000 and which is selected fromthe group consisting of aliphatic hydrocarbons and aromatic hydrocarbonshaving at least one nuclear hydrogen atom substituted by an aliphaticradical to provide a total of at least 8 aliphatic carbon atoms permolecule therein, and mixtures thereof, and (b) from about 0.5 percentto about 25 percent, based on the weight of said petroleum oil, ofcalcium hydroxide; (2) contacting said mixture with air at a temperatureof from about 125 C. to about 325 C. to effect oxidation of saidpetroleum oil and reaction of said calcium hydroxide with the oxidizedpetroleum oil; (3) continuing the oxidation for a time sufiicient toincorporate from about 0.05 percent to about 3.0 percent by weight, ofcalcium into the oxidized petroleum oil; (4) reacting the product from(3) with from about 5 percent to about 20 percent by weight, based onthe weight of the petroleum oil charged in (1), of P 3 at a temperatureof from about 75 C. to about 150 C. to form a phosphorus, sulfurandcalcium-containing product; (5) providing a mixture of the reactionproduct from (4) with from about 2 percent to about 25 percent byweight, based on the petroleum oil charged in (1), of calcium hydroxide,and water, at a temperature below the boiling point of water; (6)substantially completely dehydrating the mixture formed in (5); and (7)subjecting the dehydrated mixture to filtration to remove insolublestherefrom.

References Cited in the file of this patent UNITED STATES PATENTS2,631,129 Waugh Mar. 10, 1953 2,773,861 Musselman Dec. 11, 19562,830,949 Berger et al. Apr. 15', 1958 2,864,846 Gragson Dec. 16, 1958

1. CUTTING OIL COMPOSITION CONSISTING ESSENTIALLY OF ABOUT 94 PERCENT BYWEIGHT OF MINERAL OIL, ABOUT 3 PERCENT BY WEIGHT OF (A) A SULFURIZEDLARD OIL CONTAINING ABOUT 15 PERCENT BY WEIGHT OF SULFUR, AND ABOUT 3PERCENT BY WEIGHT OF (B) AN OIL-SOLUBLE, PHOSPHORUS-, SULFUR- ANDCALCIUM-CONTAINING OXIDIZED HYDROCARBON REACTION PRODUCT PRODUCED BY THEMETHOD WHICH COMPRISES THE STEPS OF: (1) FORMING A MIXTURE COMPRISING(A) A PETROLEUM OIL HAVING A MOLECULAR WEIGHT OF FROM ABOUT 200 TO 1000AND WHICH IS SELECTED FROM THE GROUP CONSISTING OF ALIPHATICHYDROCARBONS AND AROMATIC HYDROCARBONS HAVING AT LEAST ONE NUCLEARHYDROGEN ATOM SUBSTITUTED BY AN ALIPHATIC RADICAL TO PROVIDE A TOTAL OFAT LEAST 8 ALIPHATIC CARBON ATOMS PER MOLECULE THEREIN, AND MIXTURESTHEREOF, AND (B) FROM ABOUT 0.5 PERCENT TO ABOUT 25 PERCENT, BASED ONTHE WEIGHT OF SAID PETROLEUM OIL, OF CALCIUM HYDROXIDE; (2) CONTACTINGSAID MIXTURE WITH AIR AT A TEMPERATURE OF FROM ABOUT 125*C. TO ABOUT325*C. TO EFFECT OXIDATION OF SAID PETROLEUM OIL AND REACTION OF SAIDCALCIUM HYDROXIDE WITH THE OXIDIZED PETROLEUM OIL; (3) CONTINUING THEOXIDATION FOR A TIME SUFFICIENT TO INCORPORATE FROM ABOUT 0.05 PERCENTTO ABOUT 3.0 PERCENT BY WEIGHT, OF CALCIUM INTO THE OXIDIZED PETROLEUMOIL; (4) REACTING THE PRODUCT FROM (3) WITH FROM ABOUT 5 PERCENT TOABOUT 20 PERCENT BY WEIGHT, BASED ON THE WEIGHT OF THE PETROLEUM OILCHARGED IN (1), OF P2S5, AT A TEMPERATURE OF FROM ABOUT 75*C. TO ABOUT150*C. TO FORM A PHOSPHORUS-, SULFUR- AND CALCIUMCONTAINING PRODUCT; (5)PROVIDING A MIXTURE OF THE REACTION PRODUCT FROM (4) WITH FROM ABOUT 2PERCENT TO ABOUT 25 PERCENT BY WEIGHT, BASED ON THE PETROLEUM OILCHARGED IN (1), OF CALCIUM HYDROXIDE, AND WATER, AT A TEMPERATURE BELOWTHE BOILING POINT OF WATER; (6) SUBSTANTIALLY COMPLETELY DEHYDRATING THEMIXTURE FORMED IN (5), AND (7) SUBJECTING THE DEHYDRATED MIXTURE TOFILTRATION TO REMOVE INSOLUBLES THEREFROM.